JP7235697B2 - Reactive UV Absorber, Production Method Thereof, and UV/Electron Beam Curing Coating Agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a reactive ultraviolet absorber, a method for producing the same, and an ultraviolet/electron beam curable coating agent.

Conventionally, many ultraviolet absorbers such as benzophenone-based compounds, benzotriazole-based compounds, and triazine-based compounds are commercially available. These ultraviolet absorbers are added to paints, coating agents, inks, plastic materials for molding, etc. for the purpose of improving properties such as light resistance and weather resistance. However, since these UV absorbers are non-reactive low-molecular weight compounds, when they are added to paints or coating agents, they bleed out from the formed coating film or sublimate due to heat during drying or molding. sometimes Furthermore, when the coating film is exposed to a solvent or chemicals, the ultraviolet absorber is likely to be eluted from the coating film, making it difficult to maintain properties such as light resistance and weather resistance.

Therefore, various proposals have been made in order to maintain properties such as light resistance of various articles and products such as coating films. For example, by adding an ultraviolet absorber having a reactive group to a paint or the like and curing the ultraviolet absorber itself as a coating component, or by using a copolymer having an ultraviolet absorbing group, the bleed-out of the ultraviolet absorber can be prevented. It has been proposed to suppress UV rays and leave UV-absorbing components in various articles and products such as coating films for a long period of time (Patent Documents 1 to 4).

Japanese Patent Application Laid-Open No. 2002-226522 Japanese Patent Application Laid-Open No. 2003-253248 JP 2012-167288 A Japanese Patent Application Laid-Open No. 2001-19711

However, even with the paints and coating agents using the ultraviolet absorbers and the like proposed in Patent Documents 1 to 4, the properties such as light resistance and weather resistance of the coating film formed are not necessarily sufficient. Needless to say, there was room for further improvement.

The present invention has been made in view of the problems of the prior art, and its object is to improve light resistance, weather resistance, scratch resistance, bleed resistance, adhesion to substrates, and the like. To provide a reactive UV absorber capable of forming a coating film having excellent properties and maintaining these properties for a long period of time. Another object of the present invention is to provide a method for producing the above-described reactive ultraviolet absorber, and an ultraviolet/electron beam-curable coating agent using the above-described ultraviolet absorber.

That is, according to the present invention, the following reactive ultraviolet absorber is provided.
[1] A reactive ultraviolet absorber represented by the following general formula (1).

（前記一般式（１）中、Ｒは、相互に独立に、炭素数１～１０のアルキレン基、炭素数６以上のシクロアルキレン基、アリーレン基、又はアルキルアリーレン基を示し、Ａは、相互に独立に、水素原子又は１以上の（メタ）アクリロイルオキシ基を有する任意の有機基を示し、Ｂは、水素原子又は１以上の（メタ）アクリロイルオキシ基を有してもよい任意の有機基を示す）

(In the above general formula (1), R are each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group, and A is mutually independently represents a hydrogen atom or any organic group having one or more (meth)acryloyloxy groups, B represents a hydrogen atom or any organic group optionally having one or more (meth)acryloyloxy groups show)

[2] In the general formula (1), R is each independently a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylmethylene group, or a butylmethylene group, and A and B are each independently , hydrogen atom, 3-(meth)acryloyloxy-2-hydroxypropyl group, 3-hydroxy-4-(meth)acryloyloxy-cyclohexylmethyl group, 4-(meth)acryloyloxy-3-hydroxycyclohexylmethyl group, Or the reactive ultraviolet absorber according to [1] above, which represents a 4'-(meth)acryloyloxybutoxy-2-hydroxypropyl group (provided that A and B have less than two hydrogen atoms).
[3] The reactive ultraviolet absorber according to [1] or [2], which has two or more (meth)acryloyloxy groups in one molecule.

Further, according to the present invention, there is provided the following method for producing a reactive ultraviolet absorber.
[4] A method for producing a reactive ultraviolet absorber according to any one of [1] to [3] above, which comprises a compound (I) represented by the following general formula (I), and 3-(meta) At least one selected from the group consisting of acryloyloxy-1,2-epoxypropane, (meth)acryloyloxy(3,4-epoxycyclohexyl)methane, and (meth)acryloyloxy-2-(2-epoxymethoxy)butyl A method for producing a reactive ultraviolet absorber, comprising the step of reacting a compound (II) with 1 mol of the compound (I), and reacting the compound (II) in an amount of more than 2 mol times and not more than 3 mol times. .

（前記一般式（Ｉ）中、Ｒは、相互に独立に、炭素数１～１０のアルキレン基、炭素数６以上のシクロアルキレン基、アリーレン基、又はアルキルアリーレン基を示す）

(In general formula (I) above, each R independently represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group.)

Furthermore, according to the present invention, there is provided an ultraviolet/electron beam curable coating agent shown below.
[5] An ultraviolet/electron beam curable coating agent containing 0.1 to 50% by mass of the reactive ultraviolet absorber according to any one of [1] to [3].
[6] The UV/electron beam-curable coating agent according to [5], which is for outdoor use.
[7] The UV/electron beam-curable coating agent according to the above [5] or [6], which further contains an organic pigment.

According to the present invention, it is possible to form a coating film that is excellent in properties such as light resistance, weather resistance, scratch resistance, bleed resistance, and adhesion to a substrate, and that maintains these properties over a long period of time. A reactive UV absorber capable of preparing a coating agent can be provided. Further, according to the present invention, it is possible to provide a method for producing the above-described reactive ultraviolet absorber, and an ultraviolet/electron beam-curable coating agent using the above-described ultraviolet absorber.

<Reactive UV absorber>
Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. The reactive ultraviolet absorber of the present invention is a compound represented by the following general formula (1). The details of the reactive ultraviolet absorber of the present invention are described below.

（前記一般式（１）中、Ｒは、相互に独立に、炭素数１～１０のアルキレン基、炭素数６以上のシクロアルキレン基、アリーレン基、又はアルキルアリーレン基を示し、Ａは、相互に独立に、水素原子又は１以上の（メタ）アクリロイルオキシ基を有する任意の有機基を示し、Ｂは、水素原子又は１以上の（メタ）アクリロイルオキシ基を有してもよい任意の有機基を示す）

(In the above general formula (1), R are each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group, and A is mutually independently represents a hydrogen atom or any organic group having one or more (meth)acryloyloxy groups, B represents a hydrogen atom or any organic group optionally having one or more (meth)acryloyloxy groups show)

Since the ultraviolet absorbing group of conventional ultraviolet absorbers is a large molecular chain having a structure grafted to a polymer chain, the formed coating film tends to be soft. In addition, when the bond between the polymer chain and the UV absorbing group is cut, a single molecule derived from the UV absorbing group tends to bleed out. On the other hand, the reactive UV absorber of the present invention has a UV absorbing group of 2,4,6-tris(2-hydroxyphenyl)-1,3,5-triazine group (hereinafter referred to as "triphenyltriazine group ”), and has a structure in which a plurality of reactive groups are bonded to a triphenyltriazine group. Therefore, even if one of the bonds derived from a plurality of reactive groups is cut, the remaining bonds are retained, effectively suppressing bleeding. In addition, since triphenyltriazine is incorporated in the main skeleton, the rigidity of the aromatic ring is utilized and the physical properties of the coating film can be improved. Therefore, by using a coating agent containing the reactive ultraviolet absorber of the present invention, a coating film having excellent durability can be formed.

In the reactive ultraviolet absorber of the present invention, a plurality of organic groups containing reactive groups are grafted from the triphenyltriazine group, which is an ultraviolet absorbing group. Therefore, these multiple organic groups are easily soluble and compatible with solvents, monomers, and the like used in the coating agent, so that the amount of the reactive ultraviolet absorber to be blended in the coating agent can be increased.

It is thought that when the triphenyltriazine group, which is an ultraviolet-absorbing group, is exposed to ultraviolet rays, the hydrogen atoms delocalize between the hydroxyl groups and the nitrogen atoms of the triazine ring, diffusing thermal energy and absorbing the ultraviolet rays. The maximum absorption wavelength of the triphenyltriazine group is usually in the range of 300-360 nm.

In general formula (1), each R independently represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group. Specific examples of R include alkylene groups such as methylene, ethylene, propylene, methylethylene, butylene, isobutylene, hexylene, octylene, 2-ethylhexylene, and decylene; cyclohexylene, methylcyclohexylene, trimethylcyclohexylene, and cyclohexyldimethylene. arylene groups such as phenylene and naphthylene; alkylarylene groups such as methylphenylene; and the like. Among them, R in general formula (1) is methylene (-CH ₂ -), methylmethylene (-CH(CH ₃ )-), dimethylmethylene (-C(CH ₃ ) ₂ -), ethylmethylene (- CH(CH ₂ CH ₃ )—) and butylmethylene (—CH(CH ₂ CH ₂ CH ₂ CH ₃ )—) are preferred.

In general formula (1), A's each independently represent a hydrogen atom or any organic group having one or more (meth)acryloyloxy groups. Moreover, B represents a hydrogen atom or any organic group which may have one or more (meth)acryloyloxy groups. That is, the reactive ultraviolet absorber of the present invention preferably has two or more (meth)acryloyloxy groups in one molecule. When the number of (meth)acryloyloxy groups in one molecule is one, the UV-absorbing group is grafted onto the polymer chain. Bleeding may occur easily. In general formula (1), A and B are each independently a hydrogen atom, 3-(meth)acryloyloxy-2-hydroxypropyl group, 3-hydroxy-4-(meth)acryloyloxy-cyclohexylmethyl group, 4-(meth)acryloyloxy-3-hydroxycyclohexylmethyl group, or 4′-(meth)acryloyloxybutoxy-2-hydroxypropyl group (provided that, among A and B, two hydrogen atoms less than one).

In the general formula (1), any organic group represented by B (excluding a group having a (meth)acryloyloxy group) can be obtained by reacting a monofunctional epoxy compound or a polyfunctional epoxy compound with a carboxy group. The groups formed may be mentioned.

Monofunctional epoxy compounds include 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, polyethylene glycol monolauryl ether glycidyl ether, phenyl glycidyl ether, t-butylphenyl glycidyl ether and the like. By reacting these monofunctional epoxy compounds with part of the carboxy groups in the compound (I) described later, the solubility of the resulting reactive ultraviolet absorber in solvents may be improved. Examples of polyfunctional epoxy compounds include hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and the like. By reacting these polyfunctional epoxy compounds with a part of the carboxy groups in the compound (I), an oligomer type reactive ultraviolet absorber having a relatively high molecular weight can be obtained.

<Method for producing reactive ultraviolet absorber>
The reactive ultraviolet absorber of the present invention can be produced, for example, according to the method shown below. That is, the method for producing a reactive ultraviolet absorber of the present invention comprises compound (I) represented by the following general formula (I), 3-(meth)acryloyloxy-1,2-epoxypropane, (meth)acryloyl A step of reacting at least one compound (II) selected from the group consisting of oxy(3,4-epoxycyclohexyl)methane and (meth)acryloyloxy 2-(2-epoxymethoxy)butyl. Then, in the above step, compound (II) is reacted in an amount of more than 2 mol times and 3 mol times or less with respect to 1 mol of compound (I). The details of the method for producing the reactive ultraviolet absorber of the present invention are described below.

（前記一般式（Ｉ）中、Ｒは、相互に独立に、炭素数１～１０のアルキレン基、炭素数６以上のシクロアルキレン基、アリーレン基、又はアルキルアリーレン基を示す）

(In general formula (I) above, each R independently represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group.)

A compound represented by general formula (I) can be obtained by etherifying 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine. 2,4,6-Tris(2,4-dihydroxyphenyl)-1,3,5-triazine can be obtained by the Friedel-Crafts reaction of trichlorotriazine and resorcinol in the presence of aluminum chloride or the like.

Among the plurality of hydroxyl groups of 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, a hydroxyl group that does not contribute to ultraviolet absorption (hereinafter also referred to as "hydroxyl group X" for convenience) A compound (I) represented by the general formula (I) can be obtained by reacting a halogenated alkylcarboxylic acid (halocarboxylic acid) in the presence of an alkali such as sodium hydroxide or potassium carbonate. As the halocarboxylic acid, it is preferable to use a compound that is highly reactive, readily available, and relatively inexpensive. Such halocarboxylic acids include chloroacetic acid, bromoacetic acid, iodoacetic acid, 2-chloropropionic acid, 2-bromopropionic acid, 2-chlorobutyric acid, 2-bromobutyric acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, 2 -chlorovaleric acid, 2-bromovaleric acid, and the like. Then, the compound (I) represented by the general formula (I) is reacted with a compound having a group reactive with a carboxyl group and a (meth)acryloyloxy group to obtain a desired reactive ultraviolet absorber. Obtainable. The compound represented by formula (I) may be produced by a method other than the method described above, or a commercially available compound may be used.

Examples of the group capable of reacting with the carboxy group in the compound (I) to be reacted with the compound (I) represented by the general formula (I) include a hydroxyl group, an epoxy group, and a halogen-substituted alkyl group. Among them, it is preferable to use a compound having an epoxy group, such as 3-(meth)acryloyloxy-1,2-epoxypropane, (meth)acryloyloxy(3,4-epoxycyclohexyl)methane, and (meth)acryloyloxy More preferably, at least one compound (II) selected from the group consisting of 2-(2-epoxymethoxy)butyl is used. When such compound (II) is used, the reaction is mild, no by-products are produced due to desorption, and even if the catalyst remains, there is almost no problem. That is, it is preferable because it can be used as it is without purification after the reaction.

It is preferable to react more than 2 mol times and 3 mol times or less of compound (II) with respect to 1 mol of compound (I) represented by general formula (I), and 2.3 to 2.9 mol times of compound It is more preferable to react (II), and it is particularly preferable to react 2.5 to 2.8 mol times or less of compound (II). If compound (II) is reacted in an amount exceeding 3 times by mole per 1 mol of compound (I), compound (II) having an epoxy group will remain. Therefore, purification is required to remove the remaining compound (II), which complicates the process.

When the compound (I) represented by the general formula (I) is reacted with the compound (II), the epoxy group is ring-opened to form a hydroxyl group. The generated hydroxyl group can be reacted with an acid anhydride to form a half-esterified reactive ultraviolet absorber imparting alkali developability and high bleed-out resistance. Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, and cyclohexenedicarboxylic anhydride.

An isocyanate compound may be reacted with the generated hydroxyl group. For example, the solubility in a solvent can be improved by reacting a monofunctional alkyl monoisocyanate such as octadecyl isocyanate or lauryl monoisocyanate. In addition, 2-isocyanatoethyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, 2-[(3 ,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[0-(1′-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, etc. (meth)acryloyloxy group and isocyanate group The compounds may be reacted.

A catalyst is usually used when the compound (I) and the compound (II) are reacted. Examples of catalysts include boron fluoride ethyl ether complex; amines such as triethylamine and 1,4-diazabicyclo[2.2.2]octane; trialkyl phosphorus and triallyl phosphorus compounds such as triphenylphosphine; triethylbenzylammonium chloride, tetramethyl Quaternary ammonium salts such as ammonium chloride; imidazole compounds such as 2-methyl-4-ethylimidazole and 2-methylimidazole; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ethyltriphenylphosphonium bromide quaternary organic phosphates such as The amount of the catalyst is preferably 0.001 to 10 mol %, more preferably 0.1 to 5 mol %, relative to the epoxy groups.

It is preferable to react compound (I) with compound (II) in a solvent capable of dissolving compound (I) and the catalyst. Examples of solvents include aromatic hydrocarbons such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate and amyl acetate; tetrahydrofuran, dioxane, dioxolane, dimethylethylene glycol and the like. Ether-based solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. Among them, alcohol solvents, glycol solvents, amide solvents, and sulfoxide solvents are preferably used.

Compound (I) and compound (II) are reacted in the presence of a polymerization inhibitor such as methoxyphenol which is used as needed, while blowing air as needed. The reaction temperature may be, for example, within the range of room temperature to 150°C. As described above, the reaction of compound (I) and compound (II) does not produce any by-products, so the resulting solution can be used as it is as a solution of the reactive ultraviolet absorber.

<UV/Electron Beam Curing Coating Agent>
The ultraviolet/electron beam curable coating agent (hereinafter also referred to as "UVEB coating agent") of the present invention contains 0.1 to 50% by mass, preferably 0.5 to 30% by mass, of the reactive ultraviolet absorber described above. %, more preferably 1 to 20% by mass. If the content of the reactive ultraviolet absorber is less than 0.1% by mass, the resulting coating film will have a low ultraviolet absorbing ability. On the other hand, if the content of the reactive UV absorber exceeds 50% by mass, the reactive UV absorber that has not fully reacted tends to remain in the formed coating film, and the coating film may become brittle. When it is desired to improve the weather resistance (light resistance) of the coating film to be formed, the content of the reactive ultraviolet absorber in the UVEB coating agent is preferably 0.1 to 10% by mass. Further, when it is desired to improve the weather resistance (light resistance) of the base of the formed coating film, the content of the reactive ultraviolet absorber in the UVEB coating agent is preferably 1 to 50% by mass.

The UVEB coating agent can further contain conventionally known materials as other components. Other components include curing components such as monofunctional monomers, polyfunctional monomers, photocurable oligomers, and photocurable polymers, photopolymerization initiators for photocuring these curing components, the viscosity of coating agents, and An organic solvent or the like for adjusting coatability can be mentioned.

Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylates, cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, adamantyl methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, 2-ethoxyethyl (meth) acrylate , tetrahydrofurfuryl (meth)acrylate, allyl (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phthalic anhydride and 2-hydroxyethyl (meth)acrylate and and radical polymerizable monomers such as acryloylmorpholine.

Polyfunctional monomers and photocurable oligomers include neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, poly(n=2 or more) ethylene glycol di(meth)acrylate, polypropylene glycol (n=2 or more ) di(meth)acrylate, polybutylene glycol (n=2 or more) di(meth)acrylate, 2,2-bis(4-(meth)acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth ) acryloxydiethoxyphenyl)propane, trimethylolpropane diacrylate, bis(2-(meth)acryloxyethyl)-hydroxyethyl-isocyanurate, trimethylolpropane tri(meth)acrylate, tris(2-(meth)acrylate dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, bisphenol Epoxy poly (meth) acrylate such as epoxy di (meth) acrylate reacted with A type diepoxy and (meth) acrylic acid, reacting trimer of 1,6-hexamethylene diisocyanate with 2-hydroxyethyl (meth) acrylate urethane tri(meth)acrylate obtained by reacting isophorone diisocyanate with 2-hydroxypropyl(meth)acrylate; and urethane hexa(meth)acrylate obtained by reacting isophorone diisocyanate with pentaerythritol tri(meth)acrylate. ) acrylate, urethane di(meth)acrylate obtained by reacting dicyclohexyl diisocyanate and 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl in the urethanized reaction product of dicyclohexyl diisocyanate and poly(n=6 to 15) tetramethylene glycol Urethane poly (meth) acrylate such as urethane di (meth) acrylate reacted with (meth) acrylate, polyester (meth) acrylate reacted with trimethylol ethane and succinic acid and (meth) acrylic acid, trimethylol propane and Polyester poly( meth)acrylates and the like can be mentioned.

Photocurable polymers include poly(meth)acrylates, polyurethanes, polyesters, polyamides, polyimides, polyepoxy resins, etc., in which multiple (meth)acryloyloxy groups exhibiting radical polymerizability are introduced into the terminals and side chains of the polymers. and the like. Furthermore, an alkali-developable photocurable polymer having a carboxy group or the like can also be used.

Photopolymerization initiators include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone. , methylphenylglyoxylate, carbonyl compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethyl benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4 ,4-trimethyl-pentylphosphine oxide and other phosphoric acid compounds; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 and camphorquinone.

Examples of organic solvents include hydrocarbon-based solvents, alcohol-based solvents, ester-based solvents, ketone-based solvents, glycol-based solvents, glycol ester-based solvents, amide-based solvents, carbonate-based solvents, sulfoxide-based solvents, and ionic liquids. can.

Since the reactive ultraviolet absorber has a good ultraviolet absorption ability, it is possible to suppress the photodegradation of the pigment added to the UVEB coating agent due to ultraviolet rays and prevent the color change of the formed coating layer (paint film). can. That is, the UVEB coating agent preferably further contains an organic pigment. Examples of organic pigments include C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 97, 109, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 175, 180, 181, 185, 191; I. Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, 71, 73; C.I. I. Pigment Red 4, 5, 9, 23, 48, 49, 52, 53, 57, 97, 112, 122, 123, 144, 146, 147, 149, 150, 166, 168, 170, 176, 177, 180, 184, 185, 192, 202, 207, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 238, 240, 242, 254, 255, 264, 269, 272; I. Pigment Violet 19, 23, 29, 30, 37, 40, 50; C.I. I. Pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 22, 60, 64; C.I. I. Pigment Green 7, 36, 58; C.I. I. Pigment Black 7; C.I. I. Pigment White 6 and the like can be mentioned.

Two or more organic pigments can be used in combination. Methods of combining (mixing) two or more organic pigments include a method of mixing powder pigments, a method of mixing paste pigments, and a method of obtaining a solid solution by mixing during pigmentation.

UVEB coating agents further include light stabilizers such as nitroxide compounds, antioxidants such as hindered phenols, dyes, pigment dispersants, fluorescent brighteners, and leveling agents for improving the physical properties and coating properties of the coating film. , defoamer, lubricant, thickener, antistatic agent, surfactant, silane coupling agent, antioxidant, anti-yellowing agent, bluing agent, infrared absorber, adhesion promoter, antifouling agent, repellent A liquid agent, a curing catalyst, an inorganic filler such as silica, metal fine particles, and the like may be contained.

When used as an inkjet ink, the viscosity of the UVEB coating agent is preferably 50 mPa·s or less in consideration of ejection properties. When used for flow coating or dip coating, the UVEB coating agent preferably has a viscosity of 100 mPa·s or less. On the other hand, a highly viscous coating composition (high solid type) having a solid content of more than 80% by mass may be used.

When UVEB coating agent is used, it forms a coating film that has excellent properties such as light resistance, weather resistance, scratch resistance, bleed resistance, and adhesion to substrates, and that maintains these properties for a long period of time. be able to. The thickness of the coating film to be formed is preferably 0.1 to 50 μm, for example. When the thickness of the coating film is less than 0.1 μm, the coating film tends to be damaged, and the ultraviolet absorption ability may be slightly insufficient. On the other hand, when the thickness of the coating film exceeds 50 μm, the coating film may easily crack. Considering hardness, scratch resistance, long-term stable adhesion, suppression of cracks, etc., the thickness of the coating film to be formed is preferably 1 to 30 μm.

Substrates for forming coating films include, for example, various polymers, wood, fibers, ceramics, glass, metals, composites thereof, laminates thereof, and the like. In addition, in order to further improve the adhesion of the coating film, the surface of the substrate may be activated by corona treatment, plasma treatment, chemical treatment, or the like.

A coating film can be formed by applying a UVEB coating agent to the surface of a substrate, an article, or the like and then curing the coating by irradiating it with light. The UVEB coating agent can be applied to the surface of a substrate or the like by brush coating, spray coating, dip coating, flow coating, roll coating, curtain coating, spin coating, inkjet, or the like.

After heating or heating the applied UVEB coating agent to remove volatile components to form an uncured film, it may be further cured by irradiation with ultraviolet rays or electron beams. Ultraviolet rays and electron beams can be applied using light sources such as high-pressure mercury lamps, metal halide lamps, xenon arcs, carbon arcs, and LED lamps. The irradiation amount of light is, for example, preferably 100 to 10,000 mJ/cm ² , more preferably 300 to 5,000 mJ/cm ² .

UVEB coating agents are suitable for painting and coating articles for outdoor use that are exposed to light. Specifically, it is used for articles such as building materials, automobiles, agricultural materials, daily necessities, displays, plastic members such as home appliances, wood members, and glass members. can hold. Also, by using a UVEB coating agent containing a large amount of reactive ultraviolet absorber, it is possible to form an ultraviolet absorbing layer that protects the inside and lower layers from light. The UVEB coating agent is useful as a material for forming a coating layer that coats and protects the surface of packaging members such as foods, pharmaceuticals, display units, industrial reagents, and medical materials that are susceptible to photodegradation.

EXAMPLES The present invention will be specifically described below based on Examples, but the present invention is not limited to these Examples. "Parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Production of reactive UV absorber>
(Example 1: Reactive UV absorber-1 (M-RUVA-1))
A separable flask equipped with a stirrer, a thermometer, and a fractionating device was charged with the compound represented by the following formula (2) (2,4,6-tris[4-(1-octyloxycarbonyl)ethyloxy-2- Hydroxyphenyl]-1,3,5-triazine) (hereinafter also referred to as “triester”) and 20 parts of propylene glycol monomethyl ether acetate were added and homogenized. Then, 100 parts of methanol was added and stirred.

An aqueous sodium hydroxide solution prepared by putting 16 parts of sodium hydroxide and 100 parts of water in a separate container was added to the separable flask. After heating to about 80° C. to distill off the methanol, the solution was heated to 92° C. to drain off the water-containing methanol. After the content was transferred to a separating funnel, ethyl acetate was added to extract and remove organic solubles to obtain an aqueous layer.

800 parts of ion-exchanged water and the obtained aqueous layer were placed in a flask equipped with a dissolver. 46 parts of 3.5% hydrochloric acid was added with stirring, and the precipitate was obtained by filtration. The resulting precipitate was washed with water, dried and pulverized to obtain a yellow powder. The obtained powder was analyzed using a nuclear magnetic resonance apparatus (NMR) and an infrared spectrophotometer (IR), and the compound represented by the following formula (3) (2,2′,2″-[1, 3,5-triazine-2,4,6-triyltris[(3-hydroxy-4,1-phenylene)oxy]]trispropionic acid) (hereinafter also referred to as “tricarboxylic acid”).

Purity measured by high performance liquid chromatography (HLPC) using a mixed solvent of acetonitrile/water as a developing solvent was 98.8%. The maximum absorption wavelength measured with a spectrophotometer using dimethylsulfoxide as a solvent was 350 nm. The resulting tricarboxylic acid was soluble in methanol and glycols, and insoluble in tetrahydrofuran (THF), methyl ethyl ketone (MEK), and propylene glycol monomethyl ether acetate (PGMAc).

144.8 parts of propylene glycol monomethyl ether was put into a separable flask equipped with a stirrer, a thermometer, an air inlet tube and a fractionating device and stirred. 50.1 parts of the obtained tricarboxylic acid (pure content: 50 parts, 0.08 mol) was added and dissolved by heating to 50°C. After adding 0.1 parts of hydroquinone and 1.6 parts of triphenylphosphine and blowing in air weakly, 29.2 parts of 3-methacryloyloxy-1,2-epoxypropane (GMA) (2 parts per 1 mol of tricarboxylic acid .5 molar times) were added. Heated to 100° C. and allowed to react for 2 hours, by IR, the disappearance of the absorption at 909 cm ⁻¹ corresponding to the epoxy group, the formation of absorption around 3480 cm ⁻¹ corresponding to the hydroxyl group, and 1,720 cm −1 corresponding to the ester group ^. An increase in the absorption of ¹ was confirmed. It was also analyzed by gas chromatography (GC), and it was confirmed that no GMA peak was detected. Furthermore, the non-volatile content reaching a constant weight at 180° C. was 34.7%. Analyzed using NMR and IR, a reactive ultraviolet absorber-1 (M- It was confirmed that RUVA-1) was obtained. The maximum absorption wavelength was 357 nm. When the obtained M-RUVA-1 solution was added to MEK, THF, and PGMAc, respectively, it dissolved without precipitation.

(Example 2: Reactive UV absorber-2 (M-RUVA-2))
In the same manner as in Example 1 above, except that the amount of GMA was 29.2 parts (2.79 moles per 1 mole of tricarboxylic acid), the compound represented by the above formula (4) was used as the main component. As a result, a reactive ultraviolet absorber-2 (M-RUVA-2) containing the compound represented by the above formula (5) as a secondary component was obtained. The obtained M-RUVA-2 contained a larger amount of the compound represented by the above formula (4) than the M-RUVA-1 obtained in Example 1. GC analysis confirmed that no GMA peak was detected. The non-volatile content reaching constant weight at 180° C. was 35.9%. The maximum absorption wavelength was 357 nm.

(Example 3: Reactive UV absorber-3 (M-RUVA-3))
Same as in Example 1 above, except that 40.2 parts of methacryloyloxy (3,4-epoxycyclohexyl)methane (ECHMMA) (2.5 moles per 1 mole of tricarboxylic acid) was used instead of GMA. Then, a reactive ultraviolet absorber-3 (M-RUVA-3) containing a compound represented by the following formula (6) as a main component and a compound represented by the following formula (7) as a subcomponent was obtained. . GC analysis confirmed that no ECMMMA peak was detected. The non-volatile content reaching constant weight at 180° C. was 38.0%. The maximum absorption wavelength was 356 nm.

(Example 4: Reactive UV absorber-4 (M-RUVA-4))
Same as Example 1 above, except that 41.0 parts of acryloyloxy 2-(2-epoxymethoxy)butyl (GHBA) (2.56 moles per 1 mole of tricarboxylic acid) was used instead of GMA. Then, a reactive ultraviolet absorber-4 (M-RUVA-4) containing a compound represented by the following formula (8) as a main component and a compound represented by the following formula (9) as a subcomponent was obtained. . Analysis by GC confirmed that no GHBA peak was detected. The non-volatile content reaching constant weight at 180° C. was 37.4%. The maximum absorption wavelength was 356 nm.

(Example 5: Reactive UV absorber-5 (M-RUVA-5))
Except that the amount of GHBA was changed to 32 parts and 8.4 parts of 2-ethylhexyl monoglycidyl ether (EHG) was further used, in the same manner as in Example 4 described above, represented by the following formula (10) A reactive ultraviolet absorber-5 (M-RUVA-5) was obtained. Part of the 4'-(meth)acryloyloxybutoxy-2-hydroxypropyl group in the following formula (10) was a hydrogen atom (--H). Analysis by GC confirmed that neither GHBA nor EHG peaks were detected. The non-volatile content reaching constant weight at 180° C. was 37.2%. The maximum absorption wavelength was 356 nm.

(Comparative Example 1: Comparative Reactive UV Absorber-1 (R-RUVA-1))
A compound (2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl) represented by the following formula (11) was placed in a separable flask equipped with a stirrer, a thermometer, and a fractionator. Oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine)) (hereinafter also referred to as “monool”) 50 parts, PGMAc 120.8 parts , and 0.1 part of hydroquinone were added and heated to 100° C. while blowing air. A mixture of 12.4 parts 2-isocyanatoethyl methacrylate (MOI) and 12.4 parts PGMAc was added, followed by a mixture of 0.05 parts tin dilaurate and 12.4 parts PGMAc. A reaction was carried out at 100° C. for 5 hours to obtain Comparative Reactive UV Absorber-1 (R-RUVA-1) represented by the following formula (12). IR analysis confirmed the disappearance of absorption around 2,200 cm ⁻¹ corresponding to the MOI. The non-volatile content reaching constant weight at 180° C. was 29.4%. The maximum absorption wavelength was 341 nm. It was confirmed that the obtained R-RUVA-1 was dissolved in a solvent such as MEK.

(Comparative Example 2: Comparative Reactive UV Absorber-2 (R-UVA-2))
The following formula (13 ) to obtain a comparatively reactive UV absorber-2 (R-RUVA-2). The non-volatile content reaching constant weight at 180° C. was 31.7%. The maximum absorption wavelength was 340 nm.

<Production of coating agent and formation of coating film>
(Examples 6-9, Comparative Examples 3-6)
For 30 parts of urethane acrylate oligomer 1 (trade name “WR-100”, manufactured by Dainichiseika Kogyo Co., Ltd.) and 70 parts of urethane acrylate oligomer 2 (trade name “GD785”, manufactured by DIC), the produced reactive ultraviolet absorber , triester, or monool (5 parts as solids) were added. MEK was added to dilute the solid content to 50% to obtain a coating agent. The obtained coating agent was applied to a primer-treated olefin sheet or transparent PET film (100 μm) using a number 6 bar coater, dried at 60° C. for 1 minute, and then exposed to an electron beam (50 kGy, A applied voltage of 165 kv) was applied to cure the coating agent to form a coating film.

<Evaluation>
(Weather resistance test)
"Super UV test" and "QUV test" were carried out under the following conditions using the olefin sheet with the coating film formed on the surface.
[Super UV test]
Lamp type: Metal halide lamp Lamp illuminance: 50 mW/cm ²
Temperature: 63°C
Irradiation time: 20 hours Cycle: 1,000 hours of 30 seconds of shower and 4 hours of condensation [QUV test]
Lamp type: UV lamp Lamp illuminance: 0.71 W/m ²
Temperature: 60°C
Irradiation time: 4 hours Cycle: 5,000 hours of 4-hour condensation at 50°C

The 60° C. gloss retention (%) of the coating film after each test was measured. Table 1 shows the results. Also, the edge of the coating film was visually observed to evaluate the adhesion. Table 1 shows the results.

(Scratch resistance)
Steel wool was placed on the surface of the coating film formed on the olefin sheet, and reciprocated 10 times with a load of 100 g/cm ² . The appearance of the coating film after 10 reciprocations was visually confirmed to evaluate the scratch resistance. Table 1 shows the results.

(Bleed resistance)
After the PET film with the coating film formed on the surface was immersed in hot water at 60° C. for one week, the appearance of the coating film was visually confirmed. Further, the total light transmittance (absorbance at the maximum absorption wavelength) was measured before and after the immersion, and the retention rate (%) of the total light transmittance was calculated. Table 1 shows the results.

<Preparation and evaluation of UV ink>
(Example 10)
Polyester urethane acrylate (terephthalic acid/sebacic acid/ethylene glycol/neopentyl glycol copolymer (hydroxyl value: 37.4 mgKOH/g), isophorone diisocyanate, and hydroxyethyl acrylate urethane oligomer, number average molecular weight: 4,500) 50 parts, 15 parts of trimethylolpropane triacrylate, 35 parts of phenoxyethyl acrylate, 10 parts of reactive ultraviolet absorber-4 (M-RUVA-4) (as solid content), 3 parts of 2-hydroxy-2-methylpropylphenone , and 2 parts of 2,2-diethoxyacetophenone were mixed and stirred to obtain a UV ink.

After applying UV ink obtained using a number 6 bar coater to a polycarbonate plate so as to be 3 g / m ² , UV (high pressure mercury lamp 160 w / cm × 3, 50 m / min) is irradiated, UV ink was cured to form a coating film. As comparative examples, (i) a triester compound was added in place of M-RUVA-4; and (ii) M-RUVA-4 was not added; were prepared to form coating films. bottom.

A "super UV test" was performed under the following conditions using a polycarbonate plate having a coating film formed on its surface.
[Super UV test]
Lamp type: Metal halide lamp Lamp illuminance: 50 mW/cm ²
Temperature: 83°C
Irradiation time: 200 hours

The degree of yellowing of the coating film before and after the super UV test was visually confirmed and compared. (ii) The coating film formed with the UV ink of the comparative example to which M-RUVA-4 was not added turned yellow. In addition, the coating film formed with the UV ink of the comparative example to which (i) the triester compound was added was slightly yellowed and the surface was sticky. In contrast, the coating film formed with the UV ink of Example 10 did not discolor and the surface was not sticky.

<Production and evaluation of UV-curable coating agent (yellow color)>
(Examples 11 to 14)
Yellow pigments (Pigment Yellow 74 (manufactured by Dainichiseika Kogyo Co., Ltd.), Pigment Yellow 150 (manufactured by Lanxess), Pigment Yellow 155 (manufactured by Dainichiseika Kogyo Co., Ltd.), and Pigment Yellow 180 (manufactured by Dainichiseika Kogyo Co., Ltd.)) 20 parts each, 2 parts of an acidic synergist represented by the following formula (14), a graft-type basic dispersant (Synthesis Example 9 described in Japanese Patent No. 5953380, polyethylene glycol monopropylene glycol monomethyl ether monoamine (molecular weight 2000) and , a polymeric dispersant having a number average molecular weight of 17,300, a PDI of 1.41, and an amine value of 40.0 mgKOH/g, obtained by living radical polymerization of macromonomer/dimethylaminoethyl methacrylate/methyl methacrylate which is a reaction product with MOI. , 100% solids) and 70 parts of phenoxyethyl acrylate (POE) were placed in a plastic bottle. Zirconia beads (0.1 m) were loaded and dispersed with paint conditioner for 3 hours. After removing the zirconia beads, POE was added to dilute to a non-volatile content of 25%. Filtration with a filter (0.5 μm) removed coarse particles to prepare mill bases (pigment dispersions) of four types of yellow pigments.

21.6 parts of each pigment dispersion prepared, 2 parts of reactive ultraviolet absorber-5 (M-RUVA-5), 51.4 parts of 2-(2-vinyloxyethoxy) ethyl acrylate, ethylene oxide adduct trimethylol 20 parts of propane triacrylate, 3 parts of 2-hydroxy-2-methylpropylphenone, and 2 parts of 2,2-diethoxyacetophenone are mixed and homogenized, and filtered through a filter (1.0 μm) to give a yellow color. of UV curable coating agents (4 types) were obtained. As a comparative example, (iii) yellow UV-curing coating agents (four types) to which M-RUVA-5 was not added were prepared.

A transparent PET film (100 μm) that had been primed was coated with the UV-curable coating obtained using a No. 6 bar coater, and then dried at 60° C. for 1 minute. A xenon weather meter was used to irradiate ultraviolet rays for 120 hours to cure the ultraviolet curable coating agent and form a coating film. As a result, it was found that the pigment in the UV-curable coating agent of Comparative Example faded. Among the UV-curable coating agents of Examples, Pigment Yellow 74 was slightly faded, but the other pigments were almost unchanged. The viscosities of the coating agents of Examples were as low as around 5.0 mPa·s. Therefore, the coating agents of Examples are useful as inkjet inks.

The reactive ultraviolet absorber of the present invention is, for example, protective and decorative coating agents for automobiles, buildings, outer walls, ships, roads, solar power generators, etc., and packaging materials for packaging food products and pharmaceuticals. It is useful as a material to be blended in the coating agent of.

Claims (6)

A reactive ultraviolet absorber represented by the following general formula (1).

(In the above general formula (1), R are each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group, and A is mutually independently represents any organic group having one or more (meth)acryloyloxy groups, and B represents a hydrogen atom or any organic group optionally having one or more (meth)acryloyloxy groups) In the general formula (1), each R independently represents a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylmethylene group, or a butylmethylene group,
A is mutually independently 3-(meth)acryloyloxy-2-hydroxypropyl group, 3-hydroxy-4-(meth)acryloyloxy-cyclohexylmethyl group, 4-(meth)acryloyloxy-3-hydroxysiloxy a hexylmethyl group or a 4′-(meth)acryloyloxybutoxy-2-hydroxypropyl group,
B is a hydrogen atom, 3-(meth)acryloyloxy-2-hydroxypropyl group, 3-hydroxy-4-(meth)acryloyloxy-cyclohexylmethyl group, 4-(meth)acryloyloxy-3-hydroxycyclohexyl 2. The reactive ultraviolet absorber according to claim 1, which represents a methyl group or a 4'-(meth)acryloyloxybutoxy-2-hydroxypropyl group. A method for producing the reactive ultraviolet absorber according to claim 1 or 2 ,
Compound (I) represented by the following general formula (I), 3-(meth)acryloyloxy-1,2-epoxypropane, (meth)acryloyloxy(3,4-epoxycyclohexyl)methane, and (meth) a step of reacting with at least one compound (II) selected from the group consisting of acryloyloxy 2-(2-epoxymethoxy)butyl,
A method for producing a reactive ultraviolet absorber, wherein more than 2 mol times and 3 mol times or less of the compound (II) is reacted with 1 mol of the compound (I).

(In general formula (I) above, each R independently represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 6 or more carbon atoms, an arylene group, or an alkylarylene group.) An ultraviolet/electron beam curable coating agent containing 0.1 to 50% by mass of the reactive ultraviolet absorber according to claim 1 or 2 . The UV/electron beam curable coating agent according to claim 4 , which is used outdoors. 6. The UV/electron beam curable coating agent according to claim 4 or 5 , further comprising an organic pigment.